Sol–gel material as a support of organometallic catalyst for ethylene polymerization

Korach, Łukasz; Czaja, Krystyna; Kovaleva, N. Yu.

doi:10.1016/j.eurpolymj.2007.11.037

Cited by 13 publications

(12 citation statements)

References 15 publications

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“…In earlier investigations [4,5] we have found that the sol-gel method offered a high versatility and flexibility in production of potential carrier materials with a different structure and morphology. Besides immobilization of transition metal compound, such supported catalysts appeared to be active in low-pressure ethylene polymerization.…”

mentioning

confidence: 99%

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Białek

Korach²,

Czaja³

2007

Polimery

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Silica-type materials with different structure and morphology, synthesized using sol-gel process, were applied as a carriers of organometallic catalytic systems (VOCl 3 /AlEt 2 Cl) for ethylene-1-hexene copolymerization. Carrier materials, prior to immobilization of the vanadium compound, were pre-treated using two modes: one-step thermal modification and two-steps modification including additional reaction with AlEt 2 Cl. It was found that the carrier's type and way of it's modification significantly influence the catalysts activity in ethylene-1-hexene copolymerization as well as the incorporation of higher 1-olefin. The favourable effect of two-step modification mode on the catalysts activity and 1-hexene incorporation efficiency was proposed.

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mentioning

confidence: 99%

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Białek

Korach²,

Czaja³

2007

Polimery

Self Cite

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“…According to the studies of Hammawa and Wanke,27 the fragmentation mechanism of less fragile catalysts is the shrinking core, whereas highly friable catalysts follow the continuous bisection fragmentation model. Time profile activity of this catalyst as an important feature is related to fragmentation of porous supports as reported by Knoke et al28 Although better understanding of these behaviors would offer significant support to catalyst design and development, very little has been done to investigate and constructing the relation between support‐catalyst‐polymerization behavior and polymer properties 29, 30. The ability of the support to fragment is an essential requirement for an applicable catalyst system as fragmentation down to the nanometer scale guarantees a high activity and productivity.…”

Section: Introductionmentioning

confidence: 92%

Studying the effects of SiO₂ specifications and properties of (SiO₂/MgCl₂/TEOS/TiCl₄/AlEt₃) catalyst system on kinetic behavior and hydrogen responsibility of ethylene slurry polymerization

Vakili

Arabi

Mobarakeh

et al. 2010

J of Applied Polymer Sci

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A series of silica gels with different physico-chemical properties such as average pore size diameter, pore volume, attrition quality index, and bulk density were prepared, characterized, and subjected to treatment in special thermal program. Catalyst precursors were prepared by reaction of these silica gels with dibutyl magnesium (MgBu 2 ) at 50C and then addition of tetraethoxy ortho silicate and subsequent impregnation with titanium tetrachloride (TiCl 4 ). Polymerization of ethylene by these catalysts at comparable conditions and also at different P H2 /P C2 ratio was carried out; the results showed that support properties have significant influence on polymerization behaviors such as activity profile, productivity, and hydrogen responsibility. To quantitative analysis of the results, a new kinetic relation for rate-time profiles was derived, and these kinetic parameters were used to study and calculate of the effects of support specification. It was observed that trends of activity profiles were mainly affected by support properties and as well as P H2 /P C2 ratio. Interestingly enough, catalysts with different pore volume diameter show different behavior with variation of P H2 /P C2 ratio. Increasing in pore size diameter from 60 to 200 Å give raises catalyst activity by two times. Finally, mentioned variables were attributed to different particle growth and mechanism of fragmentation during polymerization.

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“…This is in accordance with the literature, which shows that AlEt 2 Cl is a highly effective modifier of silica surface and forms stable active centres of transition metal compounds. 56,57 Generally, regardless of the type of silica support as well as alkylaluminium compound used as modifier and/or activator, the heterogeneous systems without the ionic liquid were characterized by lower activities as compared to the SIL systems ( Table 2; Fig. 8).…”

Section: Activity Of Supported Catalyst Systems Without Ionic Liquidmentioning

confidence: 99%

Ethylene polymerization using vanadium catalyst supported on silica modified by pyridinium ionic liquid

Ochędzan‐Siodłak

Bihun

Olszowy

et al. 2016

Polymer International

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Vanadium catalyst systems (SIL1–3A(B)/V) for ethylene polymerization were obtained by immobilization of the Cp2VCl2 precursor (V) in the ionic liquid 1‐[3‐(triethoxysilyl)propyl]pyridinium chloride (IL), modified by AlCl3 and AlEtCl2 (A) or AlEt2Cl (B), and supported on three types of silica carrier S1–3. The properties of the ionic liquid supports were determined using Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller measurements, scanning electron microscopy and elemental analysis. The best results (above 2 tons PE (mol V)−1 (0.5 h)−1) were obtained using the catalyst system SIL3B/V. Addition of ethyl trichloroacetate is possible in the ionic liquid medium and it further increases the activity up to 7 tons PE (mol V)−1 (0.5 h)−1. In contrast, application of the imidazolium ionic liquid to the SIL system or application the analogous catalyst system without the ionic liquid results in lower activities. The obtained polyethylene (PE) is a linear polymer, with molecular weight (Mw) of over 106 g mol−1 and molecular weight distribution (Mw/Mn) in the range 1.6–1.9, and has a characteristic fluffy or fibrous shape. In contrast, the PE samples obtained using the systems without ionic liquid reveal broader Mw/Mn (2.5–3.7) and replicate the support morphology. © 2016 Society of Chemical Industry

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Sol–gel material as a support of organometallic catalyst for ethylene polymerization

Cited by 13 publications

References 15 publications

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Studying the effects of SiO₂ specifications and properties of (SiO₂/MgCl₂/TEOS/TiCl₄/AlEt₃) catalyst system on kinetic behavior and hydrogen responsibility of ethylene slurry polymerization

Ethylene polymerization using vanadium catalyst supported on silica modified by pyridinium ionic liquid

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Sol–gel material as a support of organometallic catalyst for ethylene polymerization

Cited by 13 publications

References 15 publications

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Copolymerization of ethylene with 1-hexene over vanadium catalysts immobilized on sol-gel silica

Studying the effects of SiO2 specifications and properties of (SiO2/MgCl2/TEOS/TiCl4/AlEt3) catalyst system on kinetic behavior and hydrogen responsibility of ethylene slurry polymerization

Ethylene polymerization using vanadium catalyst supported on silica modified by pyridinium ionic liquid

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Studying the effects of SiO₂ specifications and properties of (SiO₂/MgCl₂/TEOS/TiCl₄/AlEt₃) catalyst system on kinetic behavior and hydrogen responsibility of ethylene slurry polymerization